Carbohydrate products and processes therefor



March 9, 1954 K. M. GAVER ETAL 2,671,779 CARBOHYDRATE PRODUCTS'AND PROCESSES THEREFOR Filed June 8, 1948 6 Sheeiis-Sheet 1 EARBOHYDRATEI IALKA u HYDROXIDE m NON-AQUEOUS SOLVENT i ORGANIC [gamma T0 PRODUCE MONOALKALI canaonvonmc] REACTANT V v Eamon T0 Pnoouc: MONOORGANIC'CARBOHYDRATE] ALKALI HYDROXIDE m NON AOUEOUS SOLVENT I REMOVAL or WATER Emma T0 PRODUCE mouoommqmmmmu, cmsouvomfl v ORGANIC sussrn'unou REACTIONTO PRODUCE REM-m v Mouoommc, INORGANIC maonrnmrs L I Rmcnou TO PRODUCE moRcAmc cnnaouvnnns] ALmu METAL D\5.5OLVED m AMMONIA ORGANIC [REACTION T0 PRODUCE moRsAmc ALKALI CARBOHYDRATE REACTANT REACTION TO Pnooues POLYORGANIC CARBDHYDRATE INVENTOR. KENNETH M. SAVER ESTHER RLASURE BY ERH v. TIESZEN hid/7% 1a,"

ATTOR E'Y March 9, 1954 M. GAVER ETAL 2,671,779

CARBOHYDRATE PRODUCTS AND PROCESSES THEREFOR Filed June a, 1948 e Sheets-sheet 2 CARBOHYDRATE Lymu HYDROXIDE m NON-AQUEOUS soLvENfi IORGANIc REA TANT] lgsA'cTlon T0 mooucz MONOALKALI masonvbmfi IEEMZTION TO PRODUCE MONOORGANIC CARBOHYDRATEI ALKALI METAL DISSOLVED IN AMMONlA REACTION T0 PRODUCE MONOORGANIC POLYALKALI cmaouvnnnc SUBSTITUTION REACTION T PRODUCE MONOORGANIC POLYIMRGANIC CARBOHYDRATE ORGANIC REACTANT V I [REM-rum Tb PRODUCE POLYORGANIC cmaouvnrmfl INVENTOR. Fig. 2. KENNETH M. GAVER b ESTHER P. LASURE DERK Mil SZEN mm Lh- ATTORN' Y March 1954 K. M. GAVER ETAL 7 CARBOHYDRATE PRODUCTS AND PROCESSES THEREFOR Filed June 8, 19 8 6 Sheets-Sheet :s

CARBOHYDRATE ALKALI HYDROXIDE m Es. STARCH NONAQUEOUS SOLVENT L v m REACTION T0 PRgDucEmALKAu METALLIC ALKALI m SOLUTION cmsonvorwcfas STARCHATE) m LIQUID AMMONIA v a r f E REACTWN TO PRODUCE TRIALKALI cmaouvnnnflgsf STARCHATEJ r MM, cu (cwxcnoiflcuow) e 0 SUBSTITUTION REAcTwNEgo fRODUCE v mmoncnmc CARBOHYDRAT .QsTARtHhTE) ORGAmc ORGAN;

Hocu c' u(cn)(c:ow(cnom) e 3 REACTANT REACTANT J REACTION TO Pnongcs monumc REACTION TO rnooucq TRlORGANlC cmaonvom'refas. STARCHAZE) CARBOHYORATEQEG. STARCSATE) I "I l "I HOCH cn(cu-)(cnon)(cnon) c-o Roe", CH(CI+)(CHOR) (cuon)co METALLIC ALKALI IN SOLUTION IN LIQUID AMMONIA &

MQ'OCHZ CH(CH-)(CHOR)(CHOR) c suasmu'nou REACTION TO PRODUCE DIORGANIC REACTION To PROBE-ICE; POLYORGANIC MoNomoRcAmc cmsonvnmzfacfwcunz) cmaonvnnmdag STARCHATE) KENNETH M. GAVER 'BYESTHER F! LASURE DERK v. szEN March 9, 1954 K. M. GAVER ET AL ,671, 7

CARBOHYDRATE PRODUCTS AND PROCESSES THEREFOR Filed June 8, 1 948 6 Sheets-Sheet 4 [m Eoowm HYDROXIDE m NONAGUEOU$ SOLVENT] l oRsAmg HAUDE REACTION TO PRODUCEGZ-MONOSODIUM mmune R x Hocw cH(cH-)(cHoH)(cHoM c'-o soowm REACTION TO PRODUCE HYDROXIDE Z-MONOORGANI STARCHATE REMOVAL NWAQUECUS HocH c'H(cH-)(cHou)(cHoR) 3 F WATER SOLVENT v v v REACTION TO PRODUcE Z-MONOORGANIC onsamc 3-M0NosomuM sTARcHATE g E Hguos HOCHZ cH(cH- (cHo M)(cHoR) c A R x SUBSTDTUTION REACTION T0 PRODUCE Z- MONOORGANIC-3- MONOMETALLIC STARC HATE i REACTION T0 PRODUCE 2,3- DIORGANIC Sg'ARCHA E 500mm METAL r-' 1 ,n HocH cH(c|-+)(H0R")(cr1oR c795 mssowzn m AMMONIA L aa-monsmc, G-Mglosomum STARCHATE oRsAm H/mm: HQ MAOCHZCH(CH-)(H0RU)(CH0R1) e 5 v R x SUBSTITUTION REACTION TO PRODUCE REACTION T0 PRODUCE 2,3 6 2,3 D|ORGANIC -6- MONOMETALLIC STARCHATE TRIORGANIC S' I'ARCHATE INVENTOR. P19. 4- KENNETH M. GAVER ESTHER R LASURE BY DERK v. IESZEN A TTOIPNE' March 9,-' 1954 K, M: GAVER E 2,671,779

CARBOHYDRATE PRODUCTS AND PROCESSES THEREFOR Filed June 8, 1948 6 Sheets-Sheet 5 ISTARCH 500mm HYDROXiDE IN NON AQUEOUS SOLVENT REACTION TO PRooucE Z-Mouosomum MEOTAL STARCHAJE ORGANIC Horn, c'H(cH-)(cHom(cnoM5c' 0 $1? Somum METAL m SUBSTITUTION nincnou T0 PRODUCE SOLUTION m uaum z-mouoosmm STARCHATE'.

ORGANIC Ramon TO PRODUCE zfmonooncnmc METAL mugs 3,6'DISOBIUM METAOL STARCHATE H SALT r------ R MocH cH(cH-)(cHoM )(CHOR) e 0 REACTION TO PRODUCE 2,3,6 TRIORGANIC 5T CHATE SUBSTlTUTlON REACTION TO PRODUCE 2-MONOORGANIC 3,6 DIMETALUC STARCHATE INVENTOR. 9 KENNETH M. SAVER YESTHER P. LASURE B DERK v. IESZEN March 9, 1954 K. M. GAVER ET AL CARBOHYDRATE PRODUCTS AND PROCESSES THEREFOR Filed June 8, 1948 6 Sheets-Sheet 6 ALKALI METAL IN SOLUTION lN LIQUID AMMONIA ORGANIC REACTANT REACTION T0 PRODUCE ALKALI META L FDLYHEXOSE ('LGIsTARcH/WE M OCH cH(cH-)(c womcuou) E 5 I METAL SALT SUBSTITUTION REACTION o PRODUCE MMDORGANIC PoLYHExgsE ("ea STARCHATE) Rben CH(cH-)(CHOH)(CHOH) ,c' 0

SUBSTITUTION REACTION T0 PRODUCE Monomenmc PoLYnExosE (EGZSTARCHATE HEATIN a|c mumu METAL HYDROXIDE m NONAQUEOOS soLvsufl HEATING ll5c REACTION TO PRODUCE Mguooncmlc Momum new. MYHEXOSECEGSTAKHATE) REACTION To PRODUCE nqpuoonsAmc DMLKALI POLYHEXOSE (r-1c. STARCHATE) ORGANIC. REACTANTI METAL SALT METAL SALT Fussnwnon REACTION TO PRoDucE 0 Ram; H(c+)(cHoM)(c|-ioM) o SUBSTITUTION REACTlON TO mnucs G-MONOORGANIC Z-MONOMETALLIC POLYHEXOSE("E.G .STARCHATE) SUBSTITUTION REACTIor! To PRODUCE moRsAmc Pmmorosz (5.6. STARCHATE) O ROCHZ cn(c+9(cHoH)(cHoM) E 5 ALKALI METAL HYDROXIDE IN NONAQUEOUS SOLVENT IHEATINC ||sc| REACTION r0 PRODUCE Qm pRGAmc ALKALI METAL POLYHEXOSE (E5. srmcum) I METAL SALT I REACTION TO PRooycE POLYORGANIc POLYHEXOSE G. STARCHATE') Fig.6.

INVENTOR. KENNETH M. SAVER ESTHER P. LASURE V SUBSTITUTION REACTION TO PRODUCE nloRsAmc METALLlC Pgm-lsxose 'E.6.$TARCHATE) BY DERK 'v.

T szsw ATTORAZ'Y Patented Mar. 9, 1954 CARBOHYDRATE PRODUCTS AND PROCESSES THEREFOR Kenneth M. Gaver and Esther P. Lasure, Columbus, Ohio, and Derk V. Tieszen, Delmar, N. Y., assignors to Ohio State University Research Foundation, a corporation of Ohio Application June 8, 1948, Serial No. 31,696

30 Claims. 1

The invention disclosed in this application relates to new compositions of matter and new processes for the formation of such compositions. The processes described herein illustrating our invention are designed to produce new products from carbohydrates and similar compounds. Any compound having a hydroxyl or an analogous group (nitrogen or other nonmetal analogue) in a position adjacent to a carbonyl group or to a po tential carbonyl group can be considered a carbohydrate or a similar compound and when manipulated according to our processes reacts similarly. Such carbohydrates and similar compounds are herein termed carbohydric compounds or carbohydric substances which terms are hereby defined as used in this specification and claims as compounds having a hydroxyl or an analagous group (nitrogen or other nonmetal analogue) in a position adjacent to a carbonyl group or a potential carbonyl group. Our processes when applied to carbohydrates ordinarily include first the synthesis of either a monoalkali carbohydrate or a, polyalkali carbohydrate; then the substitution of an organic group or organic groups in place of the alkali substituent or substituents to block further reaction at that point; and thereafter at least a second reaction with an alkaline material to substitute one or more additional alkali groups at another position of the original compound, thus forming a-mixed organic alkali substituted product. 7

Our new processes are applicable to all types of carbohydrates such as monosaccharides, disaccharides, trisaccharides, tetrasaccharides and polyamyloses which are sometimes collectively designated as sugars; polysaccharides including polypentoses and polyhexoses, the latter including dextrins, starches, cellulose, lichenin, dextran, glycogen, etc.; conjugated saccharides including gums, glucosides and tannins; and derived saccharides. As stated above, it is also applicable to other compounds similar to carbohydrates provided such compounds have a hydroxyl group (or nonmetal analogue thereof) attached to a carbon which is adjacent to a carbonyl group or a potentially carbonyl group.

After the formation of the mixed organic alkali compound as mentioned above, the compound may, if desired, be again reacted with an organic reactant to substitute one or more organic groups in place of the alkali substituents so as to form a mixed polyorganic compound. The reaction with thealkali or such reaction and the substitution of an organic group in place of the alkali may in certain instances be repeated again.

One of the objects of ourinvention is the Prozen-233.3)

vision of new and useful processes of forming new and useful carbohydrates and similar products.

A further object of our invention is the proviother carbohydric compounds.

Further objects of our invention are (1) the.

provision of organic derivatives of polyalkali metal alcoholates of starch and other carbohydrates in which the organic substituents are selectively distributed on the various carbon groups as may be desired, and (2) the provision of processes of forming them.

Further objects and features of our invention. will be apparent from the following description, reference being had to the accompanying drawings wherein preferred forms of embodiments of the invention are clearly shown in illustration of our inventions.

In the drawings:

Fig. 1 is a diagram illustrating processes of forming mixed organic alkali carbohydrates and mixed polyorganic carbohydrates.

Fig. 2 is a similar diagram illustrating processes of forming different mixed organic alkali carbohydrates and illustrating processes of forming polyorganic carbohydrates by a different method;

Fig. 3 is a similar diagram illustrating processes of forming different mixed organic alkali carbohydrates and diorganic carbohydrates and processes of forming polyorganic carbohydrates by a still different method;

Fig. 4 is a. similar diagram illustrating similar processes of producing mixed organic-metallic starchates and of producing 2-3-6 triorganic starchates;

Fig. 5 is a similar diagram illustrating still other processes of producing metallic-organic starchates and of producing triorganic starchates; and

Fig. 6 is a similar diagram illustrating other processes of producing metallic-organic polyhexoses and starchates.

While as stated above our inventions are not limited to their application to starches, it is convenient to illustrate them as applied thereto.

Thus in carrying out certain embodiments of our process, we produce from starch certain new compounds which we have discovered and synthesized by our processes which are in the nature of alcoholatesor .ethers. of starch. To designate these compounds, we have coined the word starchate which We define as follows: Starchate means, and is used heretofore and hereafter in this specification and in the claims hereof in the sense of, a compound composed of an undetermined number of polymerized gluoopyranose units wherein a metallic atom or other inorganic group or organic radical has been sub,- stituted for each of the hydrogen atoms .of one or more of the several hydroxyl groups of the starch unit so as to form a polymerized compound which in fact is (or is at least analogous to) an alcoholate of starch, wherein oneor more of the hydroxyl hydrogens of the starch unit as. bee re a By. the substitution, as suggested above, of alkali metal atoms for one or more hydroxyl hydrogen. atoms. of the carbohydrate molecules, (or of each unit thereof. as in the case of the glucopyranose units ,of the starch molecule) we producev .a mono or poly alkali carbohydrate. We may then. treat the alkali carbohydrate so formedto produce derivatives thereof. Specifically. We may treat the alkali carbohydrates with organic reactantsto produce organic derivatives thereof. Thereafter we may again treat the compoundswith an alkali reactant to substitute one or. more. alkali metal atoms for one ,or more of theother hydroxyl hydrogen, atoms of the carbohydrate molecule (or units) to produce a mixed alkaliorganic carbohydrate. We may then reactthis-product .again with an organic reactant, different from the organic reactant previously used, to produce a mixed polyorganic. carbohydrate.

For example, we may explain by reference to the drawings more in detail some of the applications of the new processes as applied to starch. If the. carbohydrate is a starch, the initial product will be an alkali starchate. This alkali starchate'may be treated to produceanorganic starchate. The organic starchate may be again treated with an alkali reactant to produce a mixed organic alkali starchate. This mixed starohate may then be again, treated with an organicreactant to produce a mixed polyorganic starchate. According to our preferred processes when applied to starch and similar polyhexoses, the first reaction. will occur either on the numbertwo-ca-rbon atom of the glucopyranose units, oron the number two and number three carbonv atoms of the glucopyranose units.

If'the first alkali reaction to a starch unit, is on the number two carbon atom only, we may then as a second step, block that position by the reaction of the alkali starchate with an organic reactant. Then as a third step, the intermediate product formed'by the second step, may be reacted with an alkali reactant so as to substitute an alkali atom either on the number three carbon or on the number three and number six carbon atoms. Where the third step comprises the substitution of the alkali atom on the number three carbon atom only, the same or a different organic substituent may be substituted for the alkali atom by a fourth step. Where different organic groups have thus been substituted on the number two carbon atom and on the number three carbon atom, but the number six carbon atom has not been affected, then by fifth and sixth steps either a like organic group or an entirely different organic group may be substituted on the number six carbon atom. The reactions of the above described steps are illustrated in Fig. .4 and in Equations 1 to 6 inclusive below.

As suggested above the first and second step may effect the substitution on and the blocking of the number two carbon atom only, but the third step may alkalize both the number six and the number three carbon atoms and finally organic substituents may be substituted for the alkali at both positions six and three by a fourth step. This process. is illustrated by Equations 7 to 10 inclusive below and by Fig. 5.

We may cause the initial reaction to occur on the number six carbon atom. If so, we may then block that position with an organic substituent. Then a third reaction might substitute an alkali atom or atoms on the number two carbon atom or on the number two and number three carbon atoms. Thereafter the same or a different organic group may be substituted as a fourth step in place'of the alkali atom or atoms added by the third step. Then in case the number three carbon atom has not been affected, an alkali atom may be substituted on the number three carbon as a fifth step, and the same or a still different organic group may be sub.- stituted in its place as a sixth step. This process is illustrated in Fig. 6 and in Equations 11 to 16 inclusive below.

Again if as just su gested above the initial reaction is on the number six carbon atom we may then block that position with an organic substituent. Then by a third reaction we might substitute alkali atoms on both the number two and number three carbon atoms by providing for the removal of water as formed (as for example by causing the reaction to occur at about (3.). Finally an organic substituent which may be the same as or different from the first organic substituent can be substituted in place of the last mentioned alkali atom. This process is illustrated in Fig. 6 and in Equations 17 to 20 inclusive below.

Where it is desired that the substituent on the number three carbon atom be the same as the substituent on the number two carbon atom, the process may be shortened by performing the first reaction at a higher temperature or by utilizing other means to remove water so as to substitute alkali on both the two and the three carbon atoms at the same time. Thereafter these two positions may be blocked by the organic substituent and then the alkali may be substituted on the six carbon atom by the ammonia' process and an organic substituent substituted for this alkali. This process is illustrated in Equations 21 to 24 inclusive and by Fig. 3 of the drawing.

The following equations illustrate the above enumerated process steps and show the structural formulas of the intermediate and final products where R, R and R" represent different organic substituents and M represents an alkali metal'substituent.

. O H 500m .-QIWI XGHOHXOH IOL 4o 81 O. 00111005 M'OH CuHoOaM 1120 0 V H noomt moH-)(oHoH (oHoR)lo NHa 2061511005 2M- 20oHaOsM H2 0 H ROCHiLlEKOH)(CHOH)(CHOR')lO H ROCH: H (CH7)(CHOH)(CHOH) 0 ates.

C. CeHmOa M'0H e lou n H20 0.115051% 2RX otmoim m x 7 0 H E0 CHzlH(CH)(GHOR)(GHOR) 0 0 Prior to our inventions, certain processes had been discovered for the substitution of alkaline metals in starch molecules to form starchates which processes and products will be referred to hereinafter as the ammonia process and as the ammonia process starch'ate. As demonstrated in 'copending applications Serial No. 694,328 and Serial No. 707,318 and as demonstrated hereafter in this application such prior art processes produce starchates which differ essentially from all of the polysubstituted starchates disclosed and described in this application.

Likewise if glycogen, lichenin, etc. are treated in ammonia with an alkali metal, a monoalkali derivative is formed which is similar to the ammonia process starchates referred to above. These monoalkali ammonia process derivatives differ essentially from the monoalkali derivative formed by the process described in applications Serial No. 694,328, now Patent 2,609,370, and

SerialNo. 707,318, now Patent 2,518,135 (i. e.,

the process of Equation 1 above) in that the alkali metal in such ammonia process derivatives is attached to the number six carbon atom of the glucopyranose unit whereas the monoalkali starchate produced by the process of 'Equation 1 and applications is one in which the alkali metal is always attached to th number two carbon atom (i. e,, the carbon atom which is adjacent to the carbonyl group).

Referring further to the prior art process designated above as the ammoniaprocess, it may be noted that Schmid et al. (Chemical Abstracts 20:744 (1926) and Chem. Zentr. 2:1761 (1928)) produced a monoalkali derivative of starch by treating the starch in liquid ammonia with an alkali metal. Either as a final product or as an intermediate product, these investigators obtained a monoalkali compound in which the investigators concluded that the reaction occurred on the six position carbon in th glucopyranose unit of the starch molecule.

Other investigators obtained sodium hydroxide absorption compounds by dissolving starch in aqueous alkali followed by alcoholic precipitation or by treating starch with alkali metal alcohol- These compounds, however, were not 'starchate's in that the alkali metal did not enter intothestarchmolecule. l 7 7 '7 act-Irma:

With our processes We can form disubstituted and trisubstituted stare-hes, dextri-ns; glucogen, lichenin, etc. selectively. Noneofthese selected products are possibleby the prior. art processes.

Also, according to prior art methods, polysubstitut'ed productsof cellulose and ofvsimple:

sugars havebeen-prepared, as for example, as described inscherer and I-Iussey, Journal American Chemical Society, 5352344 (1931); Schorigin, Berichte 69: 713 (1936); Peterson Barry, U. S. Patent2,157,'083 (1939) British Patout No. 463,056 (1937);" Muskat, Journal of American Chemical. Society, 56:69? 61934); and Muskat, Journal of American Chemical Society, 56:2449 (1934). As'will be demonstrated below, these polysubstituted'- products of cellulose and sugar are difierentrfromthe products produced by our improved process.

Heretofore as suggested above, it has been pos sible by known processes to form compounds in 1 which metallic and nonmetallic elements, organic radicals and/or'other groups-- were-substi tuted for the hydrogen atoms ofone or, more of the hydroxyl groups of glucose or of similar sugars. However, it has not been possible to predetermine accurately which hydroxyl groups will be reacted to receive these substituted groups exceptthat where there is sui hcient alkalipresent, all' hydroxyl groups could be under certain circumstances reacted. With our process we can form disubstituted sugars and cellulose,. etc. selectively or we can if desired form polysub'stituted sugars and cellulose selectively by new processes by which we are able'i'fdesired'to predetermine diverse substituentson the various carbon atoms.

In Gaver application. Serial No. 357,995,. now abandoned, andthe continuation thereof Serial No. 707,318,- now Patent 2,518,135 and'in other sopending applications such as our applications Serial No. 694,328, now- Patent 2,609,370 and SerialNo. 781,708, new Patent 2,572,923, there are disclosed inventions relating to nonometallic starchates. (bothalkali and nonalkali) ;.to polyalkali starchates; to polymetallic starchates (nonalkali); to mono and polyorganic. starchates (sometimes called. starch ethers) to hydrolysis products of the various starchates; and: to processes of producing such. starchates and such hydrolysis products. The claimsof this application will be directed. to productsof processes for treating carbohydrates and similar materials inorder to controllably combine with such carbohydrates various and varying substituents in predetermined and controlled manner wherein there are a plurality of different substituents substituted on the various atoms or units of. the compound being treated; some of the products claimed herein. aredisclosed in copending application Serial No. 694,328, now Patent 2,699,370 but are not specifically claimed therein.

As suggested above, a greatmany workers have done extensive research in the. etherfication. of carbohydrates suchascellulose, starch, the sugars and other polysaccharides. Schmid (supra) and others reported that glycol, glucerine, glucose, lichenin, inulin and. starch reacted readily in liquid ammonia with metallic sodium to-give exclusively a. monometallic derivative. However,

Muskat (supra) reported that potassium in liquid ammonia reacts completely with all the available hydroxyl groups of the simple sugars and that completealkylation or the sugars could. be effected by' a treatment of these-metallic derivatives with an alkyl halide. Scherer and Hussey (supra) and Schorigin et alt (supra) showed and 32 that when cellulose was reacted in liquid ammoniawith an alkali metal; a trialkali metal cellulosate was formed. n the other hand none of these prior workers reported that they could obtain a pure monomethyl derivative.

Peterson et al. (Patent 2,157,083) disclosed the polyalkylation of cellulose by reacting cellulose with an alkalimetalan'd' subsequently alkylating the alkaline metal cellulose. Furthermore these inventors suggested a process for the preparation of mixed cellulose ethers wherein the cellulose molecule contains two or more different etherifying groups. Li-lienfeld (Patent 1,350,820) in 1920 disclosed a process for the preparation of alkyl ethers of starches and similar carbohydrates by treating the carbohydrates with alkyl.

salts of inorganic acids or other suitable alkyl esters in the presence of basic substances. Furthermore, he suggested processes of producing 1 mixed alkyl ethers of starch by allowing two or more inorganic acid esters or other suitable esters (difieringfrom one another as regards the alkyl radical) to act upon the starch or its derivatives. Nichols, J12, et al. according to Patent 2,405,973,

a 7 produced starch ethers by pretreating the starch with a carboxylic acid and then etheriiying the product in a substantially anhydrous reaction mixture comprising caustic alkali and the etherifying agent. In none of these prior art processes,

however, have these investigators been able to obtain any control over the positions of the glucopyranose unit towhichthe alkyl substituent is attached. ihat istosay thev methods of the past distribute alkyl radicals at random. In the processes to be described in detail herein hereafter, constant products can be obtained in which the alkyl radicals as desired are distributed on predetermined carbon atoms of the glucopyranose unit.

Many research chemists. have worked on the methylation of starch and many of them as authors have reported that they have methylated starch by mixing starch either with (a) methyl iodide and silver oxide in water; (1;) methyl sulphate and barium hydroxide; (0) methyl sulphate and sodium hydroxide; (d) alkali metal in liquid ammonia and. reacting the product with an organic halide; or (e) diazomethane. On hydrolyzing the methylated starch obtained: by such methods, there are found some dimethyl glucose, some trimethyl glucose and some tetramethyl glucose. In allof the prior art methods the alkyl groups are distributed indiscriminately. The distinction between the methylation of starch and the methylation of sugar (which is shown by the fact that the treatment of cane sugar with methyl iodide and silver oxide gives a trimethyl sucrose, while the methylation of starch by this method. gives products which have 1.5 and 2.0 methoxyl groups per glucose unit) is an indicationof this indiscriminate distribution.

On the contrary, the processes described herein controllably form mono-, di-, or trisubstituted products. In these processes if organic radicals are being substituted, the alkyl (organic) radicals are distributed as desired to form either a 2-alkyl product, a fi-alkyl product, a 2,3-alkyl product, a 2,6-alkyl product, or a 2,3,6-alkyl product wherein in each case the alkyl radicals distributed on each of the various carbon atoms may be alike or may be different as desired. Moreover, as will be shown mixed organic alkali or mixed organic nonalkali metallic starchates may also be formed as desired.

Referringnow more specifically to the drawings separately, it may be seen'that Fig. 1 illustrates a series of reactions to produce a polyorganic carbohydrate in which there are three organic substituents each of which differs from the others, it being understood, of course, that if desired we can make any two of these substituents the same or make all of the substituents the same. As shown by this figure, the carbohydrate is reacted with an alkali hydroxide in a nonaqueous solvent to produce a monoalkali carbohydrate which is then reacted with an organic reactant to produce a monoorganic carbohydrate. The monoorganic carbohydrate is then reacted with an alkali hydroxide in a nonaqueous solvent with provision for the removal of water to produce a monoorganic-monoalkali starchate. This is then reacted with a different organic reactant (it may be the same if desired) toproduce a diorganic carbohydrate. The diorganic carbohydrate is then reacted with an alkali metal dissolved in liquid ammonia to produce a diorganic alkali carbohydrate. The diorganic-alkali carbohydrate is then reacted with a different organic reactant (it may be the same if desired) to produce a polyorganic carbohydrate in which each of the three organic substituents are, if desired, different from the others. The conditions and requirements of the reactions referred to in this and in the succeeding several paragraphs will be described in detail later in this specification after general description of the processes illustrated in Figs. 2 to 6, inclusive.

As shown in Fig. 2, a carbohydrate is reacted with an alkali hydroxide in a nonaqueous solvent to produce a monoalkali carbohydrate. This is then reacted with an organic reactant to produce a monoorganic carbohydrate. The monoorganic carbohydrate is then reacted with alkali metal dissolved in liquid ammonia to produce a monoorganic-polyalkali carbohydrate. This monoorganic-polyalkali carbohydrate is then reacted with an organic reactant to produce a polyorganic carbohydrate. This process is shorterthan the process described in connection withFig. 1 but it will be noted that the organic groups which are substituted by the last reaction must be the same or their allocation will be indiscriminate. Thus although all of the controllable products which can be produced by the process described in connection with Fig. 2 can also be produced by the processes described in connection with Fig. 1 yet some of the products of the process of'Fig. 1 (such as, for example, starchates in which the organic groups of the three and six carbon atoms differ) cannot be formed by the processes described in connection with Fig. 2.

As is also described in Figs. 1 and 2, the monoorganicmono-alkali carbohydrates, the diorganic alkali carbohydrates and the monoorganic polyallrali carbohydrates may each similarly be reacted with metal or other inorganic salts to produce respectively monoorganic monoinorganic, diorganic inorganic and monoorganic po1yinorganic substituted carbohydrates.

Fig. 3 illustrates slightly difierent methods of producing a polyorganic carbohydrate and methods of producing diorganic-metallic carbohydrates. For example, a carbohydrate may be reacted with an alkali hydroxide in a suitable solvent to produce a dialkali carbohydrate. This may then be reacted with an organic reactant to produce a diorganic carbohydrate which may be reacted with a metallic alkali in solution in liquid ammonia to produce a diorganic-alkali carbohydrate. This last named product may then be.

reacted with an organic halide or other organic reactant to produce a polyorganic carbohydrate. Alternately, the dialkali carbohydrate may be reacted with metallic alkali in solution in liquid ammonia to produce a polyalkali carbohydrate which may in turn be reacted with an organic reactant to produce a polyorganic carbohydrate. It will be noted, however, that this last polyorganic carbohydrate will have all of the organic substituents alike and while such products may be produced by the process described in connection with Figs. 1 and 2 and by the process first described in connection with Fig. 3; yet polyorganic carbohydrates having constituents which difier from each other cannot be produced by the process last described. It may be noted finally that either the dialkali carbohydrate or the diorganic alkali carbohydrate may be reacted as shown with a metal or other inorganic salt to produce respectively a di-inorganic carbohydrate or a diorganic inorganic carbohydrate.

The processes illustrated in Fig. 4 apply the processes of Fig. 1 to the reaction of starch and show that starch may be reacted with an alkali hydroxide in a nonaqueous solvent to produce a monoalkali starchate and this reacted with organic reactant to produce a monoorganic starchate which then can be reacted with an alkali hydroxide in a nonaqueous solvent to produce a monoorganic-monoalkali starchate as described in connection with Fig. 1. In Fig. 4 the processes of producing a diorganic-monoalkali starchate and of producing atriorganic starchate as described in connection with Fig. 1 are also shown. However, in addition this figure shows that either the monoorganic-monoalkali starchate or other carbohydrate or the diorganic-monoalkali starchate or other carbohydrate may be reacted with a metal salt to produce in one case a monoorganicmonometallic carbohydrate and in the other a diorganic-monometallic carbohydrate.

Fig. 5 illustrates processes similar to Fig. 2, illustrating, however, the application of the processes specifically to the production of a 2,3,6- triorganic starchate through the application of the process to starch by the reaction thereof with sodium hydroxide, the reaction with organic halides, and the reaction with metallic sodium dissolved in liquid ammonia.

Fig. 6 illustrates similar processes of producing polyorganic carbohydrates. Therein two processes are illustrated. In both, a non-cellulose polyhexose carbohydrate is reacted with an alkali metal dissolved in ammonia to produce a monoalkali carbohydrate. This monoalkali carbohydrate is then reacted with an organic reactant to produce a monoorganic carbohydrate. In the first process illustrated this monoorganic carbohydrate is then reacted with an alkali hydroxide in a nonaqueous solvent at 81- C. to produce a monoorganic-monoalkali carbohydrate. Thereafter this monoorganic monoalkali carbohydrate is reacted with an organic reactant to produce a diorganic carbohydrate which is then reacted with an alkali hydroxide in a nonaqueous solvent at C. to produce a diorganic monoalkali carbohydrate. This diorganic monoalkali carbohydrate is reacted with an organic reactant to produce a triorganic carbohydrate. The product produced by these reactions may be exactly the same as the product produced by the reaction I described in connection with Fig. 1. However, the

order of the steps is changed and the product is obtained by a different process. In the second ll process illustrated in Fig. 6 the monoorganic carbohydrate is reacted with an alkali hydroxide in sufiicient quantity-tosubstitute two atomsof alkali and with provision for removal of water for example, at 115 C. This produces a monoorganic dialkali carbohydrate which may be reacted with an organic reactant to produce a triorganic carbohydrate. It must be noted, however, that these last mentioned processes illustrated in Fig. 6 do not seem to be applicable in connection with sugars, cellulose and similar compounds which when reacted with alkali metal dissolved in liquid ammonia alkalate all of the available hydroxyl groups.

Now we will describe in detail the individual steps of the various processes. In Figs. 1, 2,4 and 5, the first step disclosed involves the reaction of a starch or other carbohydrate or carbohydric substance with an alkali hydroxide in a nonaqueous solvent to produce a monoalkali starchate or carbohydrate or carbohydric substance. This step as applied to starch is described in detail in my copending applications Serial No. 694,328, now Patent 2,609,370, and Serial No. 707,318. new Patent 2,518,135 and serial No. 781,708, now Patent 2,572,923. The reactions involved in treating other carbohydrates with an alkali hydroxide as illustrated in this step of Figs. 1 and 2 are similar to the starchate reactions fully disclosed in the above entitled-applications. That is to say we have now discovered thatthis reaction takes place similarly whenever any carbohydrate (natural or synthetic) (or similar material having a plurality of hydroxyl groups one of which is adjacent to a carbonyl group in the building units of such carbohydrates or similar material) is treated as previously described. Whenever such carbohydrate or similar material is reacted with alkali hydroxide (such as the hydroxides of lithium, sodium, potassium, rubidium and cesium) in a nonaqueous solvent at a temperature from about 78-l'14 (3., the hy droxyl hydrogen which is adjacent to the carbonyl group unites with the hydroxyl of the hydroxide to form water and the alkali metal be comes attached through the oxygen of the hydroxyl to the carbon atom adjacent to the carboxyl group. 1

In the reaction of a starch as illustrated in Figs. 4 and 5, the alkali, metal atom becomes attached through the oxygen of the hydroxyl groups to the number two carbon atom to form a 2-monoalkali metalstarchate (e. g. two monosodium -metal starchate) The alkaline reacting material should have an ionization constant'of 2 l0- or greater in a solvent containing enough of the alkali in solution to produce a solution at a temperature of about 80 C. corresponding to about an 0.04N socertain to us that with such sugars, the alkali metal reacts on the carbon atom adjacent to the carbonyl group.

It has been found that any nonaqueous solvent which will .dissolve the alkali hydroxide even in small amounts is a suitablevehicle in which to carry out the reaction although all solvents may not have the same utility in the process. Following is a list of some eighty solvents which we have found suitable in this process:

ALCOHOLS USABLE Allyl Iso-amyl n-Amyl Secwamyl Tert.-amyl Anisyl Benzhydrol Benzoyl carbinol Benzyl 2,3-butanediol n-Butyl Iso-butyl Sec.-butyl Tert.-butyl Sec. but 1 carbinol B(p-Ter butyl phenoxy) e hyl Capryl Ceryl Cetyl 3-chloro-2 propanol-l Cinnamic Crotyl Cyclohexanol Decyl Diacetone Diethyl carbinol Dimethyl benzyl carbinol DiuiethyI ethynyl' carbinol Dimethyl n-pr0pyl carhinol Dimethyl isopropyl carbinol Di-n-propyl carbinol Di-iso-propyl carbinol Eth l y Z-ethyl butyl 2-ethyl hexanol Furfuryl Methallyl Methyl Methyl amyl Methyl butyl carbinol dMethyl cyclohexanol nrMethyl cyclohexanol p-Methyl cyclohexanol 2-methyl pentanoLl Methyl isopropyl carbinol 11-Nony1 n-Octyl Octanol-Z Phenyl-propy1 n-Propyl Iso-propyl Tetrahydrofurfuryl Triethyl carbinol Triphenyl carbinol VARIOUS POLYHYDRIC ALCO'HOLS USABLE Ethylene glycol Ethylene glycol monometh- '1 other Et xylene glycol monoethyl ether Ethylene glycol monobenzyl ether Ethylene glycol monobutyl ether Diethylene glycol Diethylene glycol monobenzyl ether Diefiilylene glycol monobutyl er .Di-propylene glycol Glycerol Glycerol a-n-butyl other Glycerol a,'y-dimethyl ether Glycerol a,'y-diphenyl ether Glycerol wmonomethyl ether Diethylene glycol mono- Hexamethylene glycol methyl ether 2-methyl 2,4-pentanediol Diethylene glycol mono- Propylene glycol ethyl ether Triethylene glycol Trimethylene glycol As step two of the processes'illustrated in Figs. '1, 2, 4 and 5, the monoalkali carbohydrate (e. g.

monosodium 'starchate) is reacted with an orl-O HO OHaCH(CH) (CHOH) (CHOR) OHO- A dispersing solvent may be used as desired but is unnecessary. The reactants may be agitated or not as desired. Pressure may be applied or not as desired. The monoalkali carbohydrate may be treated with the organic compound in other ways than as above specified if desired. In many of our experiments we .used organic halides, but any organic compound containing a replaceable halogen. orsirnilarly-reacting'group is satisfactory. For instance, dimethyl sulfate, amyl nitrate, nitroparaffins, organic phosphate, acetates, .benzoates, etc. are satisfactory. As fur- Acetodichlorohydrin n-Butyl chloride Allyl bromide Iso-butyl chloride Allyl chloride Sec.-butyl chloride Allyliodide Tert.-butyl chloride nAmyl bromide Iso-amyl bromide Iso-amyl chloride Tert.-amyl chloride Amylene dichloride Iso-amyl iodide Benzalacetophenone dibron-Butyl chloroacetate Iso-butyl chlorocarbonatea-Butylene bromide B-Butylene bromide Iso-butylene bromide n-Butylidene chloride n-Butyl iodide mide Iso-butyl iodide Benzal chloride Sec.-butyl iodide Benzotrichlorlde Tertebutyl iodide Beuzyl bromide Cetyl bromide Benzyl chloride Cetyl iodide Bromoacetic acid Chloral v w-Bromaceto-B-naphthone Chloroacetamide. a-Bromo-n-butyric acid Chloroacetodiethylamide 2-bromo1-chloropropane (hloroacetic acid Bromocyclohexane Chloroacetone B-Bromoethyl ether Chloroacetonitrile B-Bromoethyl phenyl ether Chlorobutane Bromoform 2-bromo-n-octane -Bromophenacyl bromide romopicrin a-Bromopropionic acid B-Bromopropionic acid 'y-Bromopropyl phenyl ether a-Bromo-n-valeric acid a-Bromoiso-valeric acid 'y-Butyl bromide Iso-butyl bromide Sec.-butyl bromide Tert.-butyl bromide ,B-Chlorobutyric acid 'y-Chlorobutyronitrile Cholorcyclohexane B-Chloroethyl acetate BChlomethyl chlorocarbonate Chloroform Chloropicrin a-Chloropropionic acid B-Chloropropionic acid B-Chloropropionitrile 'y-Chloropropyl chlorocarbona Decamethylene bromide a,B-Dibromobutyric acid 2,3-dibromopropene a,B-Dibromoprop1onic acid [Ly-Dibromoprqpyl alcohol 3,5-dibromopyr1dine a,B-Dibromos ucciI 1ic acid Dichloroacetlc acid 'y,'y'-Dichloropropyl ether ,fi Dichloroisopropyl ether tpibromohydrin Epichlorohydrin Ethyl bromide Ethyl bromoacetate Ethyl a-bromo-n-butyrate Ethyl u-bromo-n-caproate Ethyl bromomalonate Ethyl a-bromopropionate Ethyl B-bromopropionate Ethyl u-bromo-isovalerate Ethyl chloride Ethyl chloroacetate Ethyl a-chloroacetoacetate Ethyl chlorocarbonate Ethyl B-chloropropionate Ethyl dibromoacetate Ethyl dibromomalonate Ethyl dichloroa'cetate Ethylene bromohydrin Ethylene bromide Ethylene chloride Ethylene chlorobromide Ethylene chlorohydrin Ethylidene bromide Ethylidene chloride Ethyl iodide Isopropyl bromide n-Propyl chloride Isopropyl chloride Propylene bromide Propylene bromohydrin Propylene chloride Propylene chlorobromide Propylene chlorohydrm s-Tetrabromoethane s-Tetrachloroethane Trichloro-tert,-butyl alcohol 2,2,3-trichlorobutyric acid 1,1,2-trichloroethane Trichloroethylene 1,2,3-trichloropropane Triglycol dichloride Trimethylene bromide Trimethylenc bromohydrin Trimethylene chloride Trimethylene chlorobromide Tetrachloroethylene Trimethylene chlorohydrin 1,1,2-tribromoethane Triphenylchloromethane Tribromoethylene o-Xylyl bromide 1,2,3-tribromo-2-methyl m-Xylyl bromide propane D-Xylyl bromide 1,2,3-tribromopropane Trichloroacetic acid o-Xylylene bromide o Xylylene chloride and similarl reacting chemicals including especially the esters.

The alkali carbohydrate may if desired he dispersed with the organic reactant in anysuitable solvent. In addition to the solvents mentioned 14 above as solvents for the alkali hydroxides, the following dispersing solvents may also be used:

Sec.-amyl benzene n-Octane Tert.-amyl benzene Iso-Octane Benzene n-Pentane n-Butyl benzene Sec.-butyl benzene Petroleum ether Propyl benzene Tert.-butyl benzene Tetraisobutylene Cumene Tetradecane Cyclohexane Toluene 2,7-dimethyl octane 'lri-isobutylene Ethyl cyclohexane Trimethyl butane Heptane Trimethylethylene Hexane 2,2,4-trimethyl pentane Hexadecane Triphenyl methane Ligroin o-Xylene Methyl cyclohexane m-Xylene Nonane p-Xylene and various others.

The following ketones may also be used:

Acetone Methyl amyl Acetophenone Methyl butyl Anisolacetone o-Methyl cyclohexanone Benzalacetone m-Methyl cyclohexanone Benzoylacetone Methyl ethyl D ethyl Methyl hexyl Diisopropyl Methyl n-propyl Ethyl phenyl Ethyl uudecyl and various others.

The following ethers may also be used:

Methyl iso-propyl Allyl Benzyl ethyl Allyl ethyl Cholormethyl n-Amyl Dichloromethyl Iso-amyl Diethylene glycol diethyl Anethole Ethyl butyl Anisole Ethylene glycol dibenzyl Benzyl Ethylene glycol diethyl Benzylmethyl Ethyl n-Butyl benzyl Phenetole n-Butyl phenyl n-Propyl 1,4-dioxane Iso-propyl and various others.

By these various lists we do not mean to exclude any other dispersing solvents.

As indicated in Figs. 1 and 4, we have discovered that if we react the monoorganic carbohydrate resulting from the reactions of steps 2 of those figures with an alkali hydroxide in a nonaqueous solvent in the same manner as in the first step of these figures with the diiierence that the temperature is raised to C. or higher so that water formed by the reaction is removed by boiling or if other suitable provision is made for the removal of water, the process produces a monoorganic monoalkali carbohydrate. In the case of starch, this step produces a 2-monoorganic, 3-monoalkali starchate having a formula The same solvents as are used in step 1 are suitable; the same alkali hydroxides are suitable. The alkaline reacting material should have an ionization constant of 2X10- or greater in a solvent containing enough of the alkali in solution to produce an alkaline solution corresponding to a sodium hydroxide solution at a temperature of 115 C. There may be agitation or not as desired. The reaction should continue for a period of one hour or longer. There must, however, be provision for removal of water formed in the reaction. This is most important and the stricter requirements for the removal of water together with the higher temperature distinguish the requirements of this step from the requirements of step 1. It is essential as stated that the water evolved in the reaction be removed as rapidly as formed. Therefore only those solvents boiling at 115 C. or more appear now to have any utility as solvents in the reaction except in special cases where some other means 7 tion.

have been devised to remove the water. At 115 C. the water is removed by boiling or distilla- At temperatures below 115 C. special means must be provided for removing the water.

The fourth step illustrated in Figs. 1 and 4 is similar to the second step thereof. It comprises the reaction of the product of the third step with an organic reactant. This may be the same organic reactant as is used in connection with the second step or it may be a different organic reactant. It may be any of the organic halides or similar reactants mentioned above in connection with step 2. Where the initial carbohydrate is a starch as is illustrated in Fig. 4, during the treatment illustrated in the fourth step, there is a reaction to produce a 2,3-diorganic starchate having a formula of In this step as in the preceding step the temperature should be kept at 115 C. or higher and precaution should be taken to prevent water contamination.

The first step of the process disclosed in Fig. 3 is slightly different. If, as indicated in Fig. 3 the carbohydrate is initiall reacted with a similar alkali hydroxide in a nonaqueous solvent under the conditions described in the last paragraph, that is, at a temperature of 115 C. or with special provisions for the removal of water, a dialkali carbohydrate is produced as the first step in the process. However, with such modified process step, the organic radicals which are substituted preferably should be alike. If two different organic radical are substituted, the substitution will be indiscriminate.

The second step of the process illustrated in Fig. 3 is similar to the second and fourth steps of Figs. 1 and 4 as described above with the difference that sufficient organic reactant must be supplied to allow two moles thereof to react with each unit of the carbohydrate. Thereby a diorganic carbohydrate is produced. It may be noted that this diorganic carbohydrate may also be produced by the longer process disclosed in Fig. 1 (Fig. 4 where starch is reacted). However, both organic substituents will preferably in the process disclosed in Fig. 3, be the same whereas in the processes disclosed in Figs. 1 and 4 the organic substituents may, if desired, be different, and the position of such different substituents may be controlled. Thus while all of the preferred products which may be produced by the process disclosed in Fig. 3, may be produced by the process disclosed in Fig. 1 (or Fig. 4) yet the process disclosed in Fig. 3 will not produce all of the products which may be produced by the process disclosed in Fig. 1 (or Fig. 4)

The fifth main step of the processes disclosed in Figs. 1 and 4 and the third main step of the processes disclosed in Fig. 3, comprise the reaction of the product of the preceding step with an alkali metal dissolved in liquid ammonia. As pointed out above this step is a step known in the prior art. However, we combine this step with the previous steps of these processes and the combinations become new processes because they involve new combinations of steps some of which are old and some of which are new.

Moreover, entirely new products are obtained by these reactions. For example by these reactions (in the case of starch), we can produce a 2,3-diorganic-S-monoalkali starchate having a formula of M 'OCH2CH(CH) (CHOR) (CHOR) CHO The sixth main step of the process disclosed in Fig. 1 and in Fig. 4 is similar to the second and fourth steps of those processes. The fourth step of the process illustrated in Fig. 3 is also similar. In these steps we react the product of the preceding steps with an organic reactant. This reactant may be the same as used in the preceding step 2 of Figs. 1 and 4 or it may be the same as i used in the preceding step 2 of Fig. 3, or it may be entirely different from the reactants used in those steps. In the case of starch, we produce by this reaction a 2,3,6-triorganic starchate having a formula of The processes illustrated in Fig. 2 and Fig. 5 are in some respects similar to those illustrated in Fig. 1. However, the order of the steps of the processes disclosed in Figs. 2 and 5 are different from the order of the steps disclosed in Fig. 1 so that some new and different products ma be obtained. Also while some of the products obtained by the processes disclosed in Fig. 2 may be the same as the products obtained by the process of Fig. 1, still there are disclosed new processes for producing these same new compounds. As in the process described in connection with Fig. l, the first step of the process illustrated in Fig. 2 is the reaction of the carbohydrate with an alkali hydroxide dissolved in a nonaqueous solvent to produce a monoalkali carbohydrate. This is exactly the same step as described in connection with the process illustrated in Fig. 1. Moreover, the second step is also exactly the same and comprises the reaction of the monoalkali carbohydrate with an organic reactant to produce a monoorganic carbohydrate. The third step of the process illustrated in Fig. 2 comprises the reaction of this monoorganic carbohydrate with an alkali metal dissolved in ammonia to produce a monoorganic dialkali carbohydrate. Where starch is the carbohydrate used, the initial reaction produces (as is indicated in Fig. 5) a 2-monoalkali metal starchate having a formu- By the second step thereof a 2-m0n00rganic starchate having a formula of HOCHaCH(CH-)(CHOH)(CHOR)CHO is produced. When this monoorganic starchate is reacted with an alkali metal dissolved in ammonia, it produces a 2-monoorganic-3,6-dialkali starchate having a formula of M-oomcmcH-xcrroimcrrom'ono It will be noticed that this step three of the process disclosed in Figs. 2 and 5 is similar to step five disclosed in Fig. 1. The result however is that the alkali metal is attached in place of all of the hydrogens of all of the free hydroxyl groups of the carbohydrate. In the case of starch, the alkali metal is attached to both the number three carbon atom and the number siX carbon atom with the result that the product of step 3 is entirely diiferent from the product of .and with the same precautions. starch being the. initial compound, the final prodeither step 3 or step of the process described in connection with'Figs. 1 and 4.

Step "four of the reaction disclosed in Figs. 2 and 5 is similar to step two of the processes disclosed in those figures. ceding product is reacted with an organic reactant to produce a polyorganic carbohydrate (a *triorganic starchate in case starch is the initial compound). Thus steps two and four of the processes illustrated in Figs. 2 and 5 is the same step as steps 2, 4, and 6 of Fig. .1 as is fully described above in connection with the showings in Figs. 1 and 4 and is carried out in the same way In the case of uct of step four (as is illustrated in Fig. 5) is a 2,3,6-triorganic starchate having a formula .of

"Although the designation of the organic radicals in the formula of this 2,3,6-triorganic starchate as shown in Fig. 5 differs from the designation of the corresponding substituents of the 2,3,6-triorganic starchate produced by the first six steps of the process shown in Fig. 4 as is disclosed by comparison of the formulas, yet the product produced may be exactly the same, depending upon :the choice of the organic reactant for reaction in steps two,;fourand six of the process described in connection with Fig. 4 and of the organic reactant for reaction in steps two and four of the processes described .in connection with Fig. 6.

3, 4 and '5) mixed organic-metallic (or other inorganic) carbohydrates which may be produced according toour processes. For instancawe may react the 2-monoalkali starchates with a metallic salt or nonmetallic reactant to produce a 2-monometallic starchate, it being understood that in the formulas shown in the figures that M is used to indicate an alkali metal and M is used to indicate a nonalkali metal atom or group or nonmetall'ic atom or group. Such a 2-monometa'llic starchate maybe representedby the formula Furthermore the z-monoorganic 3-6 dialkali starchate disclosed in Fig.5 maybe reacted with a metal salt to produce a 'Z-monoorganic 3,6- dimetallic starchate'having a formula of v noomon ouonom cnomono Again the 2-monoorganic.3-monoalkali starchates shown in Fig. 4 may be reacted with .ametal salt to produce a 2-monoorganic-3-monometal; lic starchate. Also the 2-3 .diorganic (i-mono alkali starchateshown in Fig. 4 may be reacted with a metal salt to produce a .2-3 .diorganic fi-monometallic starchate. Similarly the monoorganic monoalkali carbohydrates, the monoo-rganic dialkali carbohydrates and -the-diorga-nic monoalkali carbohydrates shown in Figs. 1. 2 and That is to say the pre- 3 may be reacted with inorganic nonmetallic salts to produce monoorganic monoinorganic, diorganic monoinorganic .and .monoorganic diinorganic carbohydrates.

,In the processes illustrated in Fig. 6, the first step differs from the first step of the processes disclosed in Figs. 1 to 5, inclusive. Although certain of the same end products may be produced either by the processes disclosed in Fig. 6 or by the processes disclosed in Figs. '1 to 5, inclusive, the processes themselves are different, some intermediate products are different and some alternative processes produce some different products. The processes of Fig. 6 by reason of the change in the initial step are obviously different from V the processes described in connection with Figs.

1 to 5., inclusive. .In the main process .disclosed in Fig. 6, a carbohydrate (noncellulose polyhexose) is reacted with an alkaline metal dissolved in liquid ammonia to produce a monoalkali carbohydrate which in the case of starch has a formula of This monoalkali carbohydrate is then reacted (as previously described) with an organic reactant to produce a monoorganic carbohydrate differing from the monoorganic carbohydrates previously described in connection with Figs. 1 to 5, inclusive, but similar in some cases to some .of the products .of some of the prior .art processes. In

.case starch is the initial compound the product is a fi-monoorganic starchate having a formula .01

ROCH2CH(CH-)(CHOH)(CHOH)CHO 'It may be noted that this fi-monoorganic starchate 'd ifie-rs from the z-monoorganic starchate produced by the processes disclosed in Figs. 4 and O ROCHeiEKCH-XOHOH) ('CHOM )lHO The monoorganic monoalkali carbohydrate is in each .case reacted with an organic reactant to produce a'diorganic carbohydrate which in the case of a reaction of a starchate produces a 2,6- diorganic starchate having the formula of I o "aooniomorkxononxonon'ylno This diorganic starchate is then reacted with an alkali hydroxide in a nonaqueous solvent with provision for the removal of water and with adequate precautions against water contamination. The temperature must be raised to C. or higher so that water is driven oif by distillation or other provision must lie-made for the removal of water. This produces a diorganic monoalkali carbohydrate. Entire case of the reaction of a hydrate may be produced.

i such different process.

19 starchate the product is a 2,6-diorganic, 3-monoalkali starchate having a formula of ROCHzCH (CH-) (CI-M (CHOR) CHO By reaction with an organic reactant as in the processes previously described a triorganic carbo- In the case of a starchate the product is a 2-3-6-triorganic starchate having a formula of Although this formula may appear different from 1 that of the products produced by the previously described processes, yet it may define exactly the same products which may thus be produced by Also as indicated in the drawing of Fig. 6 the monoorganic monoalkali 'carbohydrate thereof may be reacted with an inorganic salt (as for example a metal salt) to 'produce a monoorganic monoinorganic carboreacted to produce a polyorganic carbohydrate in which all of the substituents except the first are preferably the same. In the case of starch this will produce a 2-3-6-triorganic starchate having a formula of The monoorganic dialkali carbohydrate may be .use in combination with certain old processes. .For instance, after obtaining a 2-organic starchate, a 2,3-organic starchate, a 2,6-organic starchate all the remain ng free hydroxyl groups may be reacted (l) by any convenient etherifying method or (2) by any other means to form derivatives of the free hydroxyls.

The following examples illustrate the application of the processes of our invention to produce ,polyorganic carbohydrates and illustrate a few of the products which may be synthesized by the processes of our invention.

Example I.-Preparation of Z-ethyl, 3-n-propyl, 6-n-butyl starchate In a 1000 ml. three-necked flask fitted with an efiicient agitator, a thermometer and a reflux condenser, the following is placed:

100 grams of starch 22 grams of sodium hydroxide .500 ml. butanol This mixture is heated to 85 C. for two hours with vigorous agitation. We filter on suction, wash with butanol and then with toluene. The

products, at this stage are a 2-sodium starchate and water in solution and if desired can be used directly. The starchate product was however, dried to separate the 2-sodium starchate. The 2-sodium starchate must be protected from moisture and carbon dioxide during filtration, processing and drying. Drying was eifected in a vacuum at temperatures below C.

The sodium starchate so prepared is suspended with ethyl bromide in anhydrous toluene according to the following proportions:

100 grams of the sodium starchate 200 ml. toluene 100 ml. of ethyl bromide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is filtered ofi and the product repeatedly extracted hot with anhydrous butanol to remove the sodium bromide formed. This purified product which is an ethyl starchate is washed with anhydrous toluene and then dried.

In a 1000 ml. Claissen flask fitted with an efficient agitator and a thermometer the following are placed:

100 grams of ethyl starchate 20 grams of sodium hydroxide Z50 ml. butanol We slowly distill with vigorous agitation until the distillation temperature ceases to rise (or when the temperature reaches 118 C.) We filter hot with elaborate precautions to avoid contamination by moisture and wash twice with anhydrous butanol then with anhydrous toluene.

ii'he product at this stage is a 2-ethyl, 3-sodium starchate and can be used directly. (The dry product is unstable.)

The ethyl sodium starchate prepared as above is suspended with n-propyl bromide in anhydrous toluene according to the following proportions:

100 grams of ethyl sodium starchate 200 ml. toluene 100 ml. of n-propyl bromide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is decanted (or filtered) off and the product repeatedly extracted hot with anhydrous butanol to remove the sodium bromide formed. This purified product is a 2-ethyl, 3-npropyl starchate and is then washed with anhydrous toluene and then dried.

A 1000 m1. three-necked flask fitted with an efiicient agitator, an ammonia inlet and a vent, and immersed two inches in a dry ice-acetone bath, is used.

Dry ammonia gas is passed into the flask until 500 ml. of liquid ammonia have been condensed. Twenty-five grams of dry 2-ethy1, 3-n propyl starchate are introduced which soon disperses in the liquid ammonia under the influence of agitation. Add sodium wire piece-wise until the mixture turns blue (3.5 to 3.7 grams). The excess sodium, indicated by the blue color, was destroyed by small amounts of carbon dioxide.

The ammonia is removed by evaporation and the product is a Z-ethyl, B-n-propyl, 6-sodium starchate.

The ethyl n-propyl sodium starchate so prepared is suspended in anhydrous toluene according to the following proportions:

100 grams starchate 200 m1. toluene 100 ml. n-butyl bromide This mixture is then :placed in 1a 1000 .ml. bomb, sealed tight andautoclaved at 100 C. for about iourhours. The supernatant liquid is decanted off and the product repeatedly extracted hot with anhydrous butanol to remove the sodium bromide formed. This purified product which 'is Z-ethyl, 3-n-propyl, e-n-butyl starchate is washed with anhydrous toluene and dried.

Example II.Preparation of 2n-butyl,'3-n-,pro-

pyZ,6-ethyl starchate We prepared a 1000 ml. three-necked flask fitted with an efiicient agitator, an ammonia "inlet and a vent, and immersed two inches a dry ice-acetone bath.

Dry ammonia gas is passed into the rfiask until 500 ml. of liquid ammonia have been conxlenscd. We introduced 25 grams of dry starch which soon dispersed in the liquid ammonia ".un-

This purified product is a d-monoethyl starchate which is washed with anhydrous toluene and then dried.

In a 1000 ml. three-necked flask fitted with an eflflcient agitator, a thermometer and a reflux condenser, weplace the following:

100 grams of 6-monoethyl starchate 22 grams of sodium hydroxide 500 m1. butanol We heat this .mixture to 85 C. :Iior two hours with vigorous agitation. We filter .on suction, wash with butanol and then with toluene. The product, at this stage can be used directly for conversion to the organic starchate. The prodnot however, dried to produce a 2-sodium-6- ethyl starchate. The 2-sodium-6-ethyl starchate must be protected from moisture'and (carbon dioxide during filtration, processing and drying. Drying was eirect'ed in a vacuum at temperatures below 100C. M

The sodium ethyl starchate prepared :asdescribed above is suspended with .n-butyl bromide in anhydrous toluene in the following propore tions:

100 grams of the sodium ethyl-starchate 200 m1. toluene 100 m1. ofn-butyl bromide This mixture is placed in a 1000 m1; bomb (glass lined), sealed tight and autoclaved at 100 C. for aboutfour hours.

The supernatant liquid is decanted off and the product repeatedly extracted .hot with an- .hydrous :butanol to remove the Na'Br formed. This purified product is 'a- 'z nbutyl fig-fethyl :starchate which is washed with anhydrous toluene and then dried.

.In a 1000 ml. Claissen flask fitted with anefficient agitator and a thermometer we lace the following:

grams of 2-n-buty'l6-ethy1 starchate 20grams of sodium hydroxide 750 ml. butanol We slowly distil with vigorous :agitation until the distillation temperature ceases to rise (or when the temperature reaches 118 0.)... We filter hot with elaborate precautions to avoid contamination by moisture and wash twice with anhydrous butanol then with anhydrous toluene.

The product at this stage is :a 2-n-butyl-3- sodium-G-ethyl starchate. The dry product is unstable.

The starchate prepared as described above is suspended "with n-propyl bromide in anhydrous toluene in the .followingproportions:

100 grams .of the .n-"butyl sodium ethyl starchate 200 ml. toluene 100ml. of then-.propyl bromide This mixture is placed in a 1000 ml. bom'b (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is decanted oh and the product repeatedly extracted hot with anhydro-us butanol to remove the NaBr formed. This purified product is a2-n-butyl, B-propyl, 6- ethyl starchate. It is then washedjwith anhydrous toluene and then dried.

Example III.--Pre 5ardticm of ii-ethyl, 'd-b'enayl,

d-isopropy'l starc'hate We prepared a .1000 :ml. three-necked flask .fitted with-an efficient agitator, an ammonia inlet and a vent, and immersed two inches in a dry iceacetone bath.

Dry ammonia gas is passed into the flask until 500 ml. of liquid ammonia have been condensed. We introduced 25 grams of dry starch which soon dispersed in the liquid ammonia under the influence of agitation. Sodium wire is added piece-wise until the mixture turns blue (3.5 to 3.7 grams). The excess sodium, indicated by the blue color, is destroyed by small amounts of carbon dioxide.

The ammonia is removed by evaporation and the product is .a 6-monosodium starchate.

The sodium starcha'tessopr'epared is suspended with isoprop yl bromide in anhydrous toluene in the following proportions:

100 grams of the sodium starchate 200 m1. toluene .100 ml. of isopropyl' bromide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight andautoc'lavedat100 C. for about four hours.

The-supernatant liquid is decanted off and the product repeatedly extract'ed hdt'with anhydrous butanol to remove theNaBr .formed. This purified product is a fi-monoisopropyl starchate which is washed with anhydrous toluene and then dried. v p

' In a"10 0'0 ml. three-necked flask fitted with an eificient agitator, athermometer and a reflux condenser, we place the following:

100 grams of. -monoisopropyl sstarchate .22 grams of sodium hydroxide .500 m1. :butan'ol y We heat this mixture to 85 C. for two hours with vigorous agitation. We filter on suction, wash with butanol and then with toluene. The prod not, at this stage can be used directly in the next step. The product was, however, dried to produce a dry 2-sodium fi-isopropyl starchate. The 2-sodium B-isopropyl starchate must be protected from moisture and carbon dioxide during filtration, processing and drying. Drying was effected in a vacuum at temperatures below 100 C.

The sodium isopropyl starchate so prepared is suspended within anhydrous ethyl bromide toluene in the following proportions:

100 grams of the sodium isopropyl starchate 200 m1. toluene 100 ml. of ethyl bromide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is decanted oif and the product repeatedly extracted hot with anhydrous butanol to remove the NaBr formed. This purified product is a Z-ethyI-G-isopropyl starchate which is washed with anhydrous toluene and then dried.

In a 1000 m1. three-necked flask fitted with an efi'icient agitator, a thermometer and a reflux condenser we place the following:

100 grams of 2-ethyl-6-isopropyl starchate 750 ml. sodium hydroxide 100' ml. benzyl chloride We heat this mixture at 95 to 105 C. for four hours with vigorous agitation. We neutralize the reaction mixture with HCl (1:1) and concentrate to a sirup under a vacuum. We take up the ether in alcohol and purify in the usual manher. The product is a 2-ethy1,3-benzyl,6-isopropyl starchate.

Example IV.-Prepamtion of 2-n-pro'pyl,3-

isopropyl, fi-benzyl starchate In a 1000 ml. three-necked flask fitted with an eflicient agitator, a thermometer and a reflux condenser, we place the following:

100 grams of starch 22 grams of sodium hydroxide 500 ml. butanol We heat this mixture to 85 C. for two hours with vigorous agitation. We filter on suction, wash with butanol and then with toluene. The products at this stage are a 2-sodium starchate and water in solution and can be used directly if desired. The product was, however, dried to separate 2-sodium starchate. The 2-sodium starchate must be protected from moisture and carbon dioxide during filtration, processing and drying. Drying was effected in a vacuum at temperatures below 100 C.

The sodium starchate so prepared is suspended with n-propyl bromide in anhydrous toluene in the following portions:

100 grams of the sodium starchate 200 ml. toluene 100 m1. of the n-propyl bromide This mixture is placed in a 1000' ml. bomb (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

. The supernatant liquid is decanted ofl and the product repeatedly extracted hot with anhydrous butanol to remove the NaBr formed. This purified product which is a n-propyl starchate is 24 washed with anhydrous toluene and then dried.

In a 1000 ml. Claissen flask fitted with an efiicient agitator and a thermometer the following are placed:

100 grams of n-propyl starchate 20 grams of sodium hydroxide 750 ml. butanol Slowly distil with vigorous agitation until the distillation temperature ceases to rise (or when the temperature reaches 118 C.). Filter hot with elaborate precautions to avoid contamination by moisture and wash twice with anhydrous butanol then with anhydrous toluene.

The product, at this stage, is a Z-n-propyl, 3-sodium starchate and can be used directly. (The dry product is unstable) The n-propyl, sodium starchate so prepared is suspended with isopropyl bromide in anhydrous toluene in the following proportions:

100 grams of the n-propyl sodium starchate 200 ml. toluene 100 ml. of isopropyl bromide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is decanted off and the product repeatedly extracted hot with anhydrous butanol to remove the NaBr formed. This purified product is a 2-n-pr0pyl, 3-isopropyl starchate and is washed with anhydrous toluene and then dried.

In a 1000 ml. three-necked flask fitted with an efiicient agitator, a thermometer and a reflux condenser, we place the following:

100 grams of 2-n-propyl, 3-isopropyl starchate 750 ml. 20% sodium hydroxide 100 ml. benzyl chloride We heat this mixture at to 105 C. for four hours with vigorous agitation. We neutralize the reaction mixture with HCl (1 :1) and concentrate to a sirup under a vacuum. We take up the ether in alcohol and purify in the usual manner.

Example V.--Preparation of Z-methyl, 3-isopropyl, 6-n-propyl starchate A 1000 ml. three-necked flask fitted with an eflicient agitator, an ammonia inlet and a vent, and immersed two inches in a dry ice-acetone bath is prepared.

We pass dry ammonia gas into the flask until 500 ml. of liquid ammonia have been condensed. We introduce 25 grams of dry starch which soon disperses in the liquid ammonia under the in fluence of agitation. We add sodium wire piecewise until the mixture turns blue (3.5 to 3.7 grams). The excess sodium indicated by the blue color, is destroyed by small amounts of carbon dioxide.

' The ammonia is removed by evaporation and the product is a G-monosodium starchate.

The sodium starchate so prepared is suspended with n-propyl bromide in anhydrous toluene in the following proportions:

grams of the sodium starchate 200 ml. toluene 100 ml. of n-propyl bromide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is decanted off and the product repeatedly extracted hot with anhydrous some butanol to remove" the NaBr-f'ormedi This pun-- fied product is a- 6*mono n-propyl starchate' which is washed with anhydrous toluene and, then dried.

In a 1000 ml. three-necked fiask.ii'tted with an. efficient agitator, a thermometer and a reflux" condenser, we. place. the following.

100 grams of fi-n-pro'pyl starchate 22 grams of. sodiumhydroxide: 500ml. butanol.

Wetheat thismixture to 85 Ci for-two hourswith;

vigorous agitation. We filter on suction; wash with butanol and then with toluene. The product; at this stage can be used directly for conversion to an organic starchate. The product, was; however dried to produce'a dryz-sodium G-n-propyl starchate. The 2-sodium 6-n-propyl starchate must: be protected from.moistureandcarbon dioxide"v during filtration,.. processing and drying- Drying was efiectedlin a vacuum at .temperatures.-

below 100 C.

The sodiumzn-propylstarchate so prepared is. then suspended with methyli iodide in anhydrous toluene in thef'ollowing proportions:

100 grams of the sodium n-propy1 starchate 200 ml. toluene 100 m1. of the methyliodide This mixture is placed'in1a1000'ml'. bomb (glass. lined), sealed tight anclautoclaved at 100 C. for about four hours The supernatant liquidiisi decantedtoff andlthe product repeatedly extracted hot With anhydrous butanol to remove-theNaI formed; This-purified product is a Z-methyl, fii-n-propyl starcha-te. It

is then washed with anhydrous-toluene-and thendried.

In a1000 ml. three-neckedflask fitted. with. an

eflicient agitator and a thermometer, we. place the following:

100'grams or. 2.-methy1, fi' nepropylistarchate 20.. grams sodium. hydroxide: 75.0 mhbutanol We slowly distil with vigorous agitation until the distillation temperature ceases to rise: We"

filter hot; taking' strict precautions to' avoid contamination by moisture and washtwice with anthydrous butanol and-then once more with anhydrous toluene; The product is a-Z-methyi, 3' sodium-G-n-propyl starchate.

The starchate prepared as described aboveis suspended" with isopropyl bromide in' anhydrous toluene inthe followingproportions 100 grams of the methyl, sodium, n-propyll starchate 200. ml.. toluene 100 m1. of isopropyl bromide This mixture is placed in a 1000;mlihomb tglasslined); sealed ti'ghtrand autoclavedi atfi 100"Ci for about four hours.

The supernatant liquid is decanted off and the product repeatedly extractedihotwith anhydrous butanol to remove the NaBrformed; This purifled product is a 2-methyl,3-isopropy1.6-n-propyl starcliate; It' 'isthen' washed with anhydrous toluene and then dried.

. distillation temperature ceases to rise.

V In a 1000 ml. three-necked flask fittedtwith'am efiicient: agitator, a thermometer and a reflux condenser, we placed" the following;

100 grams of starch zz grams of sodium hydroxide 500 1111. butanol We heated this mixture to C. for two hours with vigorous agitatiom We-filte'red on suction; washed with butanol and then withtoluene: products are a z-sodiumstarchate and'water in solution; 'lhheycan: beused. directly? if? desired.

The starchate product was, however; dried. to

separate the 2-sodium starchate; TheZ-sodiurm starchate: must: be protected from moisture and carbon. dioxide during filtration, processing; and drying.v Dryingiwasiefiected in a-.vacuumat.tem-

para-tunes below C.

The-sodiums-tarchate so prepared: is suspended: with n-propyl bromide in anhydrous toluene. in the following. proportions:

,. 100 grams of the sodiumstarchate 200 m1. toluene 1'00:ml..of; nepropyllbromidei;

This mixture is placed in a" 1000 ml. bomb (glass lined), sealed tight ancf'autociaved at" 100 C. for about four hours.

The supernatant liquid is decanted off'and the. product" repeatedly extracted hot with: anhydrous; butanol: to remove theNaB'ri formed; This purrfied' product which is a: z-n-propyl" starchateis then washed" with" anhydrous toluene" and is their dried'i In a 1000-1111". Clai'ssen flask fitted with an efliecient agitator and a thermometer; we place the following;

100 grams. of 2v-n-propyl starchate 20 grams of sodium hydroxide 750ml. butanol.-

We-slhwIydistil with vigorous-agitation until the" We filter hot with elaborate; precautions to avoid con-tami nation by moisture and wash twice with anti-W drous butanol and then withmnhydrious: toluene; The product is a 2-n-propyl,3-sodium starchate.

. rhezdry productis unstable;)

The starchate so prepared is then suspended with methyl iodide in anhydrous tolirenein the following proportions-z IO'O'grams-of then-propyl sod'iumstarchate 20.0 ml. toluene 100ml; of. theimethyliodide This mixture is plaoed in 'a 1000-ml. some (glass lined), seale'd tight andautoclave'd at 100'( for-- about four hours;

The supernatant liquid-- is decanted oifand-the product repeatedly extracted hot with anhydrous: butanol to remove the NaI formed. This purified product is a 2-n-propyl,3-methyl starchate. It is 65? then washed with anhydrous tolueneand" then dried;

We prepared a 1000 ml. three-necked flask" fittedwithan efficient agitator, an ammonia inlet and a vent, and immersed? inches irra Dry'Ice' acetone bath.

We passed dry ammonia gas into the" flask until 500 ml.- of liquid ammonia have been'eon densed'. We introduced" 25 grams-of dry starch which soon dispersed int'he liquid-ammonia under the-influence of agitation. Sodiuinwire is added Thepiece-wise until the mixture turns blue (3.5 to 3.7 grams). The excess sodium indicated by the blue color, was destroyed by small amounts of carbon dioxide.

The ammonia was removed by evaporation and the product used directly to prepare the triorganic starchate.

The starchate so prepared is then suspended with isobutyl bromide in anhydrous toluene in the following proportions:

100 grams of the starchate 200 ml. toluene 100 ml. of the isobutyl bromide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is decanted off and the product repeatedly extracted hot with anhydrous butanol to remove the NaBr formed. This purified product is a 2-n-propyl,3-methyl,6-isobutyl starchate. It is then washed with anhydrous toluene and then dried.

Example V1I.-Preparation of Z-methyl, fi-ethyl starchate We prepared a 1000 ml. three-necked flask fitted with an eificient agitator, an ammonia inlet and a vent, and immersed two inches in a Dry Iceacetone bath.

Dry ammonia gas is passed into the flask until 500 ml. of liquid ammonia have been condensed. 25 grams of dry starch is introduced which soon disperses in the liquid ammonia under the influence of agitation. Sodium wire is added piecewise until the mixture turns blue (3.5 to 3.7 grams). The excess sodium indicated by the blue color, is destroyed by small amounts of car bon dioxide.

The ammonia is removed by evaporation and the product which is a (i-sodium starchate, is used directly as follows:

The sodium starchate is suspended with ethyl bromide in anhydrous toluene according to the following:

100 grams of the sodium starchate 200 ml. toluene 100 ml. of ethyl bromide 100 grams of 6-ethyl starchate 22 grams of sodium hydroxide 500 ml. butanol We heat this mixture to 85 C. for two hours with vigorous agitation. We filter on suction, wash with butanol and then with toluene. The product is a Z-sodium, S-ethyl starchate. It can be used directly. The product was, however, dried to produce a dry 2-sodium, 6-ethyl starchate. starchate must be protected from moisture and carbon dioxide during filtration, processing and drying.) Drying was efiected in a vacuum at temperatures below 100 C.

The sodium ethyl starchate so prepared is then (The suspended with methyl iodide in anhydrous tolu-r ene in the following proportions:

100 grams of the starchate 200 ml. toluene 100 ml. of methyl iodide This mixture is placed in a 1000 ml. bomb (glass lined), sealed tight and autoclaved at 100 C. fo about four hours.

The supernatant liquid is decanted off and the product repeatedly extracted hot with anhydrous butanol to remove the NaI formed. This purified product is a Z-methyl, 6-ethyl starchate. It is then washed with anhydrous toluene and then dried.

Example VIIL-Prepamtion of polymethyl celluloses Alkali soluble cellulose preparation.Native cellulose was extracted with 17.5% aqueous caustic soda solution at 20 C. The insoluble alpha cellulose was removed by filtration through asbestos. The filtrate was neutralized whereby the beta-cellulose was precipitated. The beta form Was freed of the soluble gamma-cellulose by washing with water.

CeZZulose-oxycellulose preparation.-The purified beta-cellulose was suspended in 100 parts of 0.04 N sodium hypochlorite solution of pH 8.0 at 25 C. for 48 hours whereby a part of the cellulose was converted into oxy-cellulose. The cellulose mixture was thoroughly washed with distilled water, suspended in n-butanol and dried azeotropically with agitation by warming to C.

Sodium cellulosate preparation.-We mixed:

grams of the mixed cellulose-oxycellulose 35 grams of sodium ethylate 1800 ml. of n-butanol This mixture was reacted with vigorous agitation for two hours at 92-95 C. whereby the water in the reaction mixture was removed as the butanol azeotrope. The ethanol produced by the reaction was likewise removed. Analysis of the reaction product indicated that 8.7 grams of sodium had been reacted with the cellulose. The reaction mixture was filtered and washed with n-butanol to free it from unreacted alkali. The sodium cellulosate was returned to the reaction flask with 1800 ml. of n-butanol.

,B-Hydrowyethyl cellulosate preparation.T0 the sodium cellulosate suspension in butanol was added: 50 ml. ethylene chlorohydrin. This mixture was heated at 92-95 C. for two hours or until etherification was complete (generally less than two hours). The cellulose ether was removed by filtration, washed with butanol and finally with ether and air dried. The product was a c-hydroxyethyl cellulosate. Air dry weight 147.4 grams (dry weight 120.1 grams). Overall yield 76%.

The monoether product of this reaction is still a trihydroxy derivative and could have been re-= acted further:

1. To form the triester according to the usual accepted methods.

2. To form the triether according to the usual accepted methods.

a. By alkali methods. b. By metallic sodium methods.

-3. To form any other derivatives requiring a hydroxyl group for reaction. 

1. A SUBSTANTIALLY UNIFORMLY SUBSTITUTED GLUCOPYRANOSE POLYMER CONSISTING OF INTERLINKED AND POLYMERIZED SUBSTANTIALLY UNIFORMLY SUBSTITUTED GLUCOPYRANOSE UNITS EACH HAVING THE FOLLOWING STRUCTURAL FORMULA 